1766
Inorg. Chem. 1993,32, 1766-1772
Synthesis and Characterization of Thorium tert-Butoxide Complexes: X-ray Crystal Structures of Th( 0-t-Bu)d(py)2 and NaThz( O-t-Bu)e David L. Clark' and John G. Watkin Isotope and Nuclear Chemistry Division, Mail Stop G739, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 Received September 15, 1992
-
Two synthetic procedures have been employed for the preparation of thorium tert-butoxide complexes. Reaction of ThI4(THF)4 with 4 equiv of KO-t-Bu in THF/pyridine solution provides Th(O-t-Bu),(py)2 (1) in moderate yield. Alcoholysis of the thorium metallacycle [{(M~~S~)~N)~T~(CH~SIM~~NS~M~~)I with >4 equiv of HO-t-Bu produces the dimeric alcoholate Th2(0-t-Bu)~(HO-t-Bu)(2) in 70% isolated yield. The coordinated alcohol in 2 is readily deprotonated by employing NaN(SiMe& in hexane solution to provide hexane-soluble NaTh2(O-t-Bu)9(3) in ca. 70% yield. Formation of the trimeric complex Th3O(O-t-Bu) (4) occurs upon addition of stoichiometric amounts of H20 to refluxing toluene solutions of 2. Compounds 1-4 have been characterized by elemental analysis, 1H NMR, infrared spectroscopy, and, for 1 and 3, single-crystal X-ray diffraction. In 1, the Th atom is coordinated to four alkoxide and two pyridine ligands in a cis pseudo-octahedral fashion with average Th-0 and Th-N distances of 2.182(6) and 2.752(7) A, respectively. In 3, the NaTh,(O-t-Bu)g unit is closely related to the well-known M3Xj cluster and is best described as NaTh2(p3-O-t-Bu)2(p2-O-t-Bu)3(O-t'BU)4. Averaged Na-p3-0 and Na-p2-0 distances are 2.399(17) and 2.607(10) A, respectively. Th-O distances are 2.155(8), 2.280(10), 2.464(7), and 2.491(7) A for terminal, doubly bridging to sodium, doubly bridging to thorium, and triply bridging alkoxides, respectively. Crystal data for 1 (at 25 OC): Monoclinic space group C2/c, with a = 12.656(3) A, b = 15.326(3), c = 16.803(3) A, p = 96.43(3)', V = 3238.7(12) A', dcaj,= 1.363 g ~ m -and ~ , Z = 4. Crystal data for 3 (at 25 OC): Orthorhombic spacegroupPnma, witha = 11.170(2)A,b =25.408(5),c= 17.195(3)& V=4880.1(16)A3,dcalc=1 . 5 5 9 g ~ m - ~ , and Z = 4.
Introduction
ThCl,(HO-i-Pr),
Alkoxide complexes of the actinides were first reported in the mid 1950's, during the search for volatile complexes for uranium isotope separation. Several reviews have summarized the experimental work on thorium alkoxides from the 1950's, with a few publications on aliphatic thorium alkoxides originating from the 1960's.' Much of the early work on these complexes is due to the pioneering efforts of D. C. Bradley, whose group prepared a number of homoleptic thorium alkoxide c o m p l e ~ e s . ~The - ~ key starting material in Bradley's work was thorium isopropoxide, Th(O-i-Pr),, which was prepared from the reaction of ThC14(HO-i-Pr), with NaO-i-Pr in 2-propanol solvent as outlined in eq 1.2 Other thorium alkoxides were then conveniently prepared by alcohol interchange as outlined in eq 2.3-9 While these complexes were described nearly 40 years ago, their characterization is still limited to elemental analysis and solution molecular weight determination. Ebullioscopic molecular weight measurements in benzene indicated that aggregation of Th(OR)4 units was occurring in solution. For thorium tert-butoxide, Th(0-tB u ) ~ a, molecular complexity of 3.4 suggested a trimeric or tetrameric complex.2 ( I ) (a) Bradley, D. C. Adu. Inorg. Chem. Radiochem. 1972, 15,259. (b) Bacher, W.; Jacob, E. In Handbook on the Physics and Chemistry of the Actinides; Freeman,A., Keller, C., Eds.; Elsevier: Amsterdam, 1985; Vol. 3, Chapter 7. (c) Sattelberger, A. P.; Van Der Sluys, W. G. Chem. Reo. 1990, 90, 1027. (2) Bradley, D. C.; Saad, M. A.; Wardlaw, W. J. Chem. SOC.1954, 3488. (3) Bradley, D. C.; Saad, M. A.; Wardlaw, W. J . Chem. SOC.1954, 1091. (4) Bradley, D. C.; Chatterjee, A. K.; Wardlaw, W. J. Chem. SOC.1956, 2260. ( 5 ) Bradley, D. C.; Chatterjee, A. K.; Wardlaw, W. J. Chem. SOC.1956, 3469. (6) Bradley, D. C.; Sinha, R. P.N.; Wardlaw, W. J . Chem.SOC.1958,4651. (7) Bradley, D. C.:Kapoor, R. N.;Smith, 8 .C.J.Inorg. Nucl. Chem. 1962, 24, 863. (8) Bradley, D. C.; Kapoor, R. N.; Smith, B. C. J . Chem. SOC.1963, 1022. (9) Bradley, D. C.; Kapoor, R. N.; Smith, B. C. J . Chem. SOC.1963, 204.
+ 4NaO-i-Pr
-
HO-i-Pr
Th(0-i-Pr), Th(0-i-Pr),
+ 4HOR
HOR -+
Th(OR),
+ 4NaCl (1)
+ 4HO-i-Pr
(2)
R = Me, Et, i-Pr, n-Pr, t-Bu, etc.
-
More recent studies of thorium alkoxides have shown t h a t t r e a t m e n t of t h e thorium metallacycle [((Me3-
S ~ ) ~ N ) ~ T ~ ( C H ~ S I Mwith ~ ~4Nequiv S ~ Mof~ ~ di-isopropyl)] methanol in toluene yields colorlesscrystals of [Th(OCH-i-Pr2)4]2 in high yield.I0 The bulky di-isopropylmethoxidedimerwas shown to exist in a dynamic equilibrium at ambient temperature in hydrocarbon solution between monomeric Th(OCH-i-Pr2), and its dimer Th2(0CH-i-Pr& as outlined in eq 3.1° Th,(OCH-i-Pr,), F= 2Th(OCH-i-Pr2),
(3)
We wished to extend these studies of aliphatic thorium alkoxide chemistry to include somewhat less sterically demanding ligands and thus began an investigation of thorium complexes employing primarily tert-butoxide ligation. We report here the synthesis, physicochemical properties, and molecular structures of a series of new thorium tert-butoxide complexes prepared by a combination of metathetical and alcoholysis techniques. The relationship between these compounds and those described by Bradley in the early 1950's will be discussed.
Results and Discussion Synthesis and Reactivity. One of the most general synthetic routes for preparation of metal alkoxide complexes is the (10) Clark, D. L.; Huffman, J. C.; Watkin, J. G. J . Chem. SOC.,Chem. Commun. 1992, 266.
0020-1669/93/1332-1766%04.00/0 0 1993 American Chemical Society
Thorium tert-Butoxide Complexes
Inorganic Chemistry, Vol. 32, No. 9, 1993 1767
metathesis reaction of a metal halide and an alkali metal alkoxide. While this strategy has great utility in transition metal chemistry, retention of the alkali metal and formation of “ate” or ‘double alkoxide” complexes can be a pervasive problem in the chemistry of actinide and lanthanide metals.” Following the methodology described previously,l2 we find t h a t t h e metathesis reaction of thorium tetraiodide, Th14(THF)4,13or tetrabromide, ThBr4(THF)4,13 with potassium alkoxide salts at room temperature results in complete metathesis of the iodide or bromide ligands and provides the convenient preparation of a series of thorium alkoxide complexes and their Lewis base adducts. Since the metathesis reactions are carried out in donor solvents such as THF, any vacant coordination sites in the resulting Th(OR)4 unit are likely to be filled by solvent molecules to produce mononuclear Th(OR)4(THF), species. Thus we also employ alcoholysis reactions of thorium amide complexes in nondonor solvents (toluene or hexane) as a route to base-free Th(OR)4 units, which are then able to oligomerize until coordinative saturation is obtained. The reaction of Th14(THF)4with 4 equiv of potassium tertbutoxide in THF solution in the presence of excess pyridine produces the mononuclear bis(pyridine) adduct Th(O-t-Bu)4(py)2 (l), as outlined in eq 4. The reaction proceeds smoothly at room ThI,(THF),
+ 4KO-t-Bu
-
THFlw
Th(O-t-Bu),(py),
+ 4KI
(4)
temperature and appears to be complete within several hours. Recrystallization from hexane/pyridine gives the white, crystalline product in 22% yield based on eq 4. We note the earlier preparation by Bradley of a bis(pyridine) complex Th(0CMe~CC1~)4(py)~ and the preparation by Andersen of the related uranium complexes U[OCH(CF3)2]4(THF)2,and U[OC(CF~)~I~(THF)Z.’~ T r e a t m e n t of t h e t h o r i u m m e t a l l a c y c l e [ { ( M e 3 -
S ~ ) ~m N J ~ T ~ ( C H ~ S I Mwith ~ ~greater N S ~ Mthan ~ ~4)equiv ] of
tert-butanol in toluene solution at room temperature results in the complete substitution of alkoxide for amide and produces the dimeric alcoholate of formula Thz(O-t-Bu)s(HO-t-Bu) (2). IH NMR spectra of the products obtained by stripping the filtered reaction mixture in vacuo show that formation of 2 is essentially quantitative. Recrystallization from a cooled hexane solution at -40 OC gives 2 as a white, crystalline product in 70% yield based on eq 5. The uranium analog of 2, U2(0-t-Bu)8(HO-t-Bu), has
-
[((Me,Si),Nj,Th(CH2SiMe2NSiMe3)] +
-
toluene
>4HO-t-Bu
1/2Th2(O-t-Bu),(HO-t-Bu) + 3HN(SiMe3), ( 5 )
been prepared in a similar fashion by Sattelberger and coworkers following the alcoholysis of either [U(NEt2)4]2 or
[{(Me3Si)2N}zC(CH2SiMe2NSiMe3)].16 Compound 2 is stable in toluene-dsor benzene-d6solution at room temperature asjudged by 1 H NMR spectroscopy. The coordinated alcohol in 2 is readily deprotonated by reaction with sodium bis(trimethylsily1)amide ( 1 I ) Caulton, K. G.; Hubert-Pfalzgraf, L. G.Chem. Rev. 1990, 90, 969. (12) Clark, D. L.; Bott, S. G.; Vrtis, R. N.; Sattelberger, A. P. Inorg. Chem. 1989, 28, 1771. (13) Clark, D. L.; Frankcom, T. M.; Miller, M. M.; Watkin, J. G. Inorg. Chem. 1992, 31, 1628. (14) Stewart, J. L.; Andersen, R. A. J. Chem. SOC.,Chem. Commun. 1987, 1846. (1 5 ) Simpson, S. J.; Turner, H. W.; Andersen, R. A. J . Am. Chem. Soc. 1979, 101,7728. Simpson,S. J.; Turner, H. W.; Andersen, R. A. Inorg. Chem. 1981, 20, 2991. (16) W. G.Van Der Sluys, W. G.; Sattelberger, A. P.; McElfresh, M. W. Polyhedron 1990, 9, 1843.
in toluene or hexane solution to generate NaTh2(O-t-Bu)9(3), which may be isolated as a white crystalline solid in ca. 70% yield as outlined in eq 6.
+
toluene
+
Th2(O-t-Bu),(HO-t-Bu) NaN(SiMe,), NaTh,(O-t-Bu), HN(SiMe,), (6) Addition of stoichiometric quantities of water (2/3 equiv of H20/mol of 2) to a refluxing toluene solution of 2 leads to the formation of the oxo-capped trimeric species Th30(0-t-Bu) (4) in somewhat variable yield as outlined in eq 7. Examination
+
-
toluene
3Th2(O-t-Bu),(HO-t-Bu) 2 H 2 0 2Th30(O-t-Bu),,
+ 7HO-t-Bu
(7)
of a crude reaction product mixture by IH NMR revealed the presence of 4 and unreacted 2 as the only observable species. The trimeric species 4 may be separated from 2 by crystallization due to its lower solubility in hexane. Addition of larger quantities of water to 2 at room temperature results in the formation of a highly insoluble, flocculent white precipitate which we presume to contain thorium oxide/hydroxide species. Sattelberger has shown that the uranium analog to 4 can be prepared in a similar fashion,16 and somewhat related behavior has been observed in the cerium tert-butoxide system described by Evans, who found that both Ce(O-t-Bu)l(THF)z and NaCe2(O-t-Bu)9slowly convert to Ce30(O-t-Bu)loin toluene solution over a period of days to weeks. I Solid-state and Molecular Structures. Two thorium tertbutoxide compounds have been examined by single-crystalX-ray diffraction studies during this work Th(O-t-Bu)4(py)z (1) and NaTh2(0-t-B~)~ (3). In each case, the unit cell revealed discrete molecules. A summary of data collection and crystallographic parameters is given in Table I. Atomic positional parameters are given in Tables I1 and 111. Th(O-t-Bu)dpy*(1). Single crystals of 1suitable for an X-ray diffraction study were grown from a hexane solution by slow cooling to -40 OC. A ball and stick drawing giving the atomnumbering scheme used in the tables is shown in Figure 1. Selected bond distances and bond angles are given in Tables IV and V, respectively. Compound 1 crystallizes in the monoclinic space group C2/c with the central thorium atom lying on a 2-fold axis. The central thorium atom is coordinated to four oxygen atoms of tert-butoxide ligands and two nitrogen atoms of the pyridine ligands in a cis pseudo-octahedralarrangement as shown in Figure 1. Two different Th-0 bond lengths are seen in the molecule, 2.161(6) A for the tert-butoxide ligands trans to pyridine and 2.204(6) 8, for the tert-butoxide ligands trans to one another. These Th-O distances are similar to the averge terminal Th-0 distance of 2.154 8, seen in Th2(OCH-i-Pr2)810 and to the Th-0 distance [2.154(8) A] observed for the 2-butene-2,3-diolate ligand in the X-ray structureof ([(sS-CsMes)2Th(~-0,C2Mez)l 2}.18 The pyridine ligand exhibits a Th-N distance of 2.752(7) 8, and can be compared to the Th-N distance of 2.61(1) 8, found for the 2-(6-methylpyridyl)methylligand of T~(O-~,~-~-BU~C~H~)~(C py-6-Me)2I9and 2.754 A (av) found for the quinolinato ligands in Th(C3H7NO)(CsH6N0)4.20The Th-O-C anglesare relatively large for aliphatic alkoxideligands; the tert-butoxide ligand trans to pyridine exhibits a Th-O-C angle of 171.6(6)”, while those trans to one another are found to be 160.8(6)O. ~
~~~~~~
(17) Evans, W. J.; Deming, T. J.; Olofson, J. M.; Ziller, J. W. Inorg. Chem. 1989, 28, 4027. (18) Manriquez, J. M.; Fagan, P. J.; Marks, T. J.; Day, C. S.; Day, V. W. J . Am. Chem. SOC.1978, 100, 7112. (19) Beshouri, S. M.; Fanwick, P. E.; Rothwell, I. P.; Huffman, J. C. Organometallics 1987, 6, 2498.
1768 Inorganic Chemistry, Vol. 32, No. 9, 1993
Clark and Watkin
Table I. Summary of Crystallographic Data" compound empirical formula fw cryst dimens, mm-I space group cell dimens a, A
b, A
c,
'4
f% deg
v,A3
Z (molecules/cell) d,,~,,g cm-) abs coeff, cm-' F(000) X(Mo Ka) T, "C 28 range, deg measd reflcns cnique intensities obsd reflcns R(F) &(F) goodness-of-fit a
1
C26H28N204Th 664.5 0.15 X 0.15 X 0.25 c2/c 12.656(3) 15.326(3) 16.803(3) 96.43(3) 3238.7( 12) 4 1.363 47.89 1280 0.710 73 25 4.0-50.0 6188 2827 2570 (F > 4.0u(F)) 0.0404 0.0554 1.44
Table 111. Fractional Coordinates and Equivalent Isotropic Disdacement Coefficients" (A2) for NaThdO-r-Buh
3 C36H8109NaTh2 1145.1 0.35 X 0.25 X 0.65 Pnma
~
104~
11.170(2) 25.408(5) 17.195(3) 4880.1 (1 6) 4 1.559 63.49 2240 0.710 73 25 4.0-50.0 4795 3707 2448 (F > 6.0u(F)) 0.0376 0.0540 1.47
1 = Th(OBut)a(py)2; 3 = NaTh2(OBut)9.
Table 11. Fractional Coordinates and Equivalent Isotropic Displacement Coefficients" (A2) for Th(O+Bu)d(py)2 104~ Th(1) 0(1) C(l) C(2) C(3) C(4) O(2) C(5) C(6) C(7) C(8) N(1) C(9) C(10) C(11) C(12) C(13)
0' 1681(4) 2755(8) 3137(15) 2860(3) 3386(12) 275(6) 412(10) -281(24) 1624(26) -20(30) 305(6) 1219(9) 1479(11) 764(13) -202(12) -406(10)
i04y 1974(1) 1680(4) 1796(8) 2628(16) 1658(16) 1046(17) 2836(4) 3494(7) 4290(20) 3745(20) 3186(18) 557(5) 486(8) -231(10) -890(9) -807(7) -63(7)
104z 2500* 2387(4) 2269(7) 2484(14) 1392(10) 2698(11) 3520(4) 4101(6) 3755(17) 4243(19) 4841(20) 3506(4) 3952(6) 4423(7) 4419(9) 3974(7) 3502(7)
1
0
3
46(1) W2) 8 1(4) 244(15) 185(11) 261(15) 75(3) 80(4) 138(3) 138(3) 138(3) 65(3) 86(4) 1 13(6) 126(7) 109(6) 93(5)
~~
~
~
Th(1) O(1) C(1) C(2) C(3) O(2) C(4) (35) C(6) o(3) C(7) C(8) C(9) C(10) O(4) C(11) C(12) C(13) C(14) O(5) C(15) C(16) C(17) C(18) O(6) C(19) C(20) C(21) Na(1)
2255(1) 3673(9) 4934(14) 5281(12) 5548(19) 1771(10) 1813(17) 3160(17) 1193(15) 3239(8) 3830(17) 5041(20) 3637(36) 3305(20) 346(9) -595(13) -1096(20) -1611(19) -241(22) 2561(7) 2782(14) 2507(17) 2039(23) 4102(20) 1222(10) 842(17) 41(13) 1966(20) -212(12)
104~ 1766(1) 2500' 2500* 2013(6) 2500* 2500' 2500' 2500* 2015(6) 1273(3) 865(6) 877(11) 926(11) 351(7) 1505(4) 1166(8) 908(9) 1507(9) 792(8) 1281(3) 877(5) 1045(6) 402(7) 712(8) 2500* 2500* 2028(5) 2500* 2500*
1042
103U(eq)
69(1) 237(6) 344(9) 820(8) -421(11) -844(5) -1674(9) -1909(10) -1989(7) -724(5) -1112(9) -1014(21) -1965(13) -935(15) -196(5) -336(10) 366(11) -752(14) -1006(14) 1079(4) 1628(8) 2436(9) 1421(12) 1604(12) 746(5) 1542(11) 1661(7) 2073(10) -27 3(9)
4 2 ~ ) 46(4) 48(6) 85(6) 82(9) 50(4) 55(6) 72(8) lOO(7) 63(3) 87(7) 363(31) 337(29) 178(14) 84(4) 98(7) 158(11) 163(12) 183(14) 58(3) l34( 10) 233(17) 177(13) 54(4) 61(7) 85(6) 85(10) 168(7)
Equivalent isotropic U defined as one-third of the trace of the orthogonalized U,, tensor. Parameters maked by an asterisk were not varied.
"Equivalent isotropic U defined as one-third of the trace of the orthogonalized U,, tensor. Parameters marked by an asterisk were not varied.
NaTh2(O-t-Bu)9(2). Single crystals of 2 suitable for an X-ray diffraction study were grown from hexane solution by slow cooling to -40 OC. A ball and stick drawing giving the atom-numbering scheme used in the tables is given in Figure 2. Selected bond Figure 1. Ball-and-stick drawing of the solid-state molecular structure distances and bond angles are given in Tables VI and VII, (I), emphasizing thecis-pseudo-octahedral geometry ~fTh(O-r-Bu)~(py)z respectively. Compound 2 crystallizes in the orthorhombic space and giving the atom-numbering scheme used in the tables. group Pnma, with Na(1) and three bridging alkoxide oxygen atoms [0(1), 0(2), 0(6)]lying in the mirror plane relating the Table IV. Selected Bond Distances (A) for the T h ( O - r - B ~ ) ~ ( p y ) ~ two halves of the molecule. Crystals of 2 consist of a regular Molecule array of NaTh2(O-t-Bu)9molecular units, with no intermolecular Th( 1)-O( 1) Th(l)-0(2) 2.161 (6) 2.204(6) interactions between the Na atom of one molecule and 0 atoms Th(1)-N( 1) 0(2)-c(5) 1.401(12) 2.752(7) of adjacent molecules. The view of the structure shown in Figure C(5)-C(6) 1.576(32) 0(1)-C(1) 1.407(12) 2 was chosen to emphasize a heterometallic NaThz triangle with C( 12)-C( 13) 1.396( 16) N(I)-C(9) 1.310( 13) N ( 1)-C ( 13) 1.308(14) C(l1)-C(12) 1.366(21) two p3-ORgroups. Viewed in this fashion, the molecule is readily C(l0)-C(l1) 1.355(21) C(9)-C(10) 1.374(18) described as NaTh2(p3-O-t-Bu)2(p2-O-f-B~)3(O-f-B~)4, and this triangular representation provides a conceptual link to homoat Na-0 distances of 2.399(17) A (av) and 2.607(10) A, metallic M3 cluster units, including the Th30(O-t-Bu) cluster respectively. If one views O(4) and O(4a) as occupying axial described in this work. coordination sites on sodium, then the local coordination enviThe sodium atom is linked to the thorium atoms by two triply ronment around sodium is essentially that of a distorted trigonal bridging and two doubly bridging oxygen atoms of alkoxideligands bipyramid with one missing equatorial ligand, yet the "axial" and "equatorial" angles are distorted away from the idealized values (20) Barton, R. J.; Dabeka, R. W.; Shengzhi, H.; Mihuchuk, L. M.; Pizzey, M.; Robertson, B. E.; Wallace, W. J. Acta Crysrallogr. 1983, C39,714. due to constraints of the M3 cluster framework. Within the
Thorium tert-Butoxide Complexes
Inorganic Chemistry, Vol. 32, No. 9, 1993
C(l7a)
C(2)
Figure 2. Ball-and-stick drawing of the solid-state molecular structure of NaTh2(O-r-Bu)9(3), emphasizing the trimetallic NaTh2 unit. For clarity, tert-butyl carbon atoms are omitted from C(4) and C(19). Table V. Selected Bond Angles (deg) for the T h ( O - t - B ~ ) ~ ( p y ) ~ Molecule
O(1)-Th( 1)-0(2) O(2)-Th( 1)-N( 1) O(2)-Th( 1)-O( 1A) N( 1)-Th( 1)-O(2A) O(1)-Th(1)-N(1A) N(1)-Th(1)-N( 1A) Th( 1)-0(2)-C(5) O(2)-C( 5)-C(7) 0(2)C(5)-C(8) Th( 1)-N( 1)-C( 13) Th( 1)-N( 1)-C(9)
97.0(3) 89.8(2) 97.3(3) 165.5(2) 8 1.7(2) 75.8( 3) 171.6(6) 108.9( 14) 109.0(14) 121.4(6) 118.1(7)
Table VI. Selected Bond Distances Molecule Th( 1)-O( 1) Th( 1)-0(3) Th( 1)-0(5) Th(1)-Na(1) 0(1)-C(l) O(2)-Na(1) O(3)-C(7) O(4)-C(l1) O(5)-C( 15)
2.464(7) 2.152(8) 2.157(7) 3.380(11) 1.420(19) 2.423(17) 1.401(17) 1.381(20) 1.416(15)
O(1)-Th( 1)-N( 1) O(1)-Th(1)-O(1A) O(2)-Th( 1)-O(2A) Th( 1)-O(1)-C( 1) O(1)-C( 1)-C(3) O(l)-C(l)-C(2) O(1)-C( 1)-C(4) 0(2)-C(5)-C(6) N( 1)-C(9)-C( 10) N ( 1)-C( 13)-C( 12)
79.7 (2) 156.4(3) 104.7(3) 160.8(6) 108.1(9) 113.0(12) 107.5( 10) 106.3( 12) 122.4(11) 120.5(11)
(A) for the N a T h , ( 0 - t - B ~ ) ~ Th( 1)-0(2) Th(1)-O(4) Th(1)-O(6) Th(1)-Th(1A) 0(2)-C(4) O(4)-Na(1) O(6)-Na(1) O(6)-C( 19)
2.498(6) 2.280( 10) 2.484(7) 3.731(1) 1.428( 18) 2.607(10) 2.375( 17) 1.432(21)
Table VII. Selected Bond Angles (deg) for the NaTh2(O-?-Bu)g Molecule 0(1)-Th(l)-0(2) 0(2)-Th(l)-0(3) 0(2)-Th(l)-0(4) 0(1)-Th(l)-0(5) 0(3)-Th(l)-0(5) 0(1)-Th(l)-0(6) 0(3)-Th(l)-0(6) 0(5)-Th(l)-0(6) Th(1)-O(1)-Th(1A) Th( 1)-0(2)-C(4) Th( 1)-O( 1)-C( 1) Th( 1)-O(2)-Na(1) Th( 1)-O(2)-Th(1A) Na( 1)-0(2)-Th(1A) O(2)-C( 4)-C( 6) Th(l)-0(3)-C(7) 0(3)-C(7)-C(8) Th(l)-0(4)-Na(l) Th( 1)-O(4)-C( 11) C(11)-0(4)-Na(l) O(4)-C( 11)-C( 13) 0(4)-C(ll)-C(l4) Th( 1)-O(5)-C( 15) O(5)-C( 15)-C( 17)
69.4(3) 98.4(3) 83.6(3) 103.7(3) 95.6(3) 71.1(3) 166.2(3) 97.2(3) 98.4(4) 128.4(3) 130.7(2) 86.8(4) 96.7(3) 86.8(4) 11O.O( 9) 167.0(8) 113.0(17) 87.3(4) 158.2( 10) 114.5(9) 106.2( 15) 108.6(14) 168.1(7) 109.1(1 2)
0(1)-Th(l)-0(3) 0(1)-Th(l)-0(4) 0(3)-Th(l)-0(4) 0(2)-Th(l)-0(5) 0(4)-Th(l)-0(5) 0(2)-Th(l)-0(6) 0(4)-Th(l)-0(6) C(4)-0(2)-Na(l) 0(2)-C(4)-C(5) 0(3)-C(7)-C(9) 0(3)-C(7)-C( 10) 0(4)-C(ll)-C(12) 0(5)-C(15)-C(16) Th(l)-0(6)-C(19) C( 19)-O( 6)-Na( 1) 0(6)-C(19)-C(20) 0(2)-Na(l)-0(4) 0(2)-Na(l)-0(6) O(4)-Na( 1)-O(4A) Th(l)-0(6)-Na(l) O(6)-C( 19)-C(21) 0(4)-Na(l)-0(6) O(5)-C(l5)-C( 18)
100.7(3) 147.6(3) 100.5(3) 165.3(3) 98.2(3) 68.5(3) 82.9(3) 115.8(10) 106.9(13) 108.9(16) 111.9( 15) 114.9(14) 112.3(11) 125.8(4) 120.3( 10) 107.7(10) 78.6(4) 71.5(5) 15 1.7(7) 88.1(3) 108.8( 15) 78.5(4) 110.3(12)
heterometallicNaTh2 plane, the Th- -Th and Th- -Na distances are 3.731(1) and 3.380(11) A, respectively. Each thorium atom is bound to six alkoxide oxygen atoms located at the vertices of a distorted octahedron. Terminal tert-butoxide ligands on thorium
1769
display average Th-0 distances of 2.155(8) A and are similar to the terminal distancesfound in 1and Th2(OCH-i-Pr2)8.10Doubly bridging tert-butoxide ligands display different Th-O bond distancesdepending on whether a Th-O-Th or Th-O-Na linkage is present. A Th-O distance of 2.280(10) A is observed for the alkoxide bridging to Na, and 2.464(7) A for those alkoxides bridging to another Th atom. Triply bridging alkoxide ligands that cap the NaTh2 triangular unit display an average Th-O distance of 2.491(7) A. The structurally related uranium and cerium analogs of 3, of formulas KU2(0-t-Bu)9 and NaCez(0~ - B U have ) ~ , been reported by Cotton2' and Evans,17respectively, although the X-ray data collected for the cerium complex were of a quality which allowed only molecular connectivity to be established. By including the sodium atom in the metal count of 3, one can see that the NaTh2 triangular cluster unit is closely related to the well-known M ~ XI Icluster unit observed (lH NMR, vide infra) for compound 4, Th3O(O-t-Bu)lo, and these structural units are illustrated in 3 and 4. Both 3 and 4 contain triply bridging ligands
2
3
4
above and below the M3plane, with three doubly bridging alkoxide ligands within the M3 plane. Hence NaTh,(O-t-Bu)9 may be viewed as a simple modification of the fundamental M3Xll building block common in uranium,22y t t r i ~ m ,lanthanum,2s ~~.~~ and group VI transition metal chemistry.26As noted by Cotton,22 U30(0-t-Bu) is structurally similar, in a qualitative sense, to the M30(OR)lo cluster compounds (M = Mo, W) reported by Chisholm et a1.26 It is also apparent that the M'M209 structural unit seen in 3 is becoming more common as seen in the structures of K U * ( O - ~ - B UNaCe2(0-r-Bu)9,17 )~,~~ (DME)KZr2(O-i-Pr)9,27 [C1CdZr2(O-i-Pr)g]2,2sKBa2(OSiPh3)6(DME)2,29and [(O-iPr)BaZr2(O-i-Pr)g]2.30 Although there are no solid-state structural data for 2, we propose a confacial bioctahedral geometry in analogy to the MTh2(0R)9 unit as illustrated in 2. The proton attached to the bridging alcoholate is shown for accounting purposes only. IH NMR data reveal that the proton on the alcoholate ligand is scrambling rapidly between alkoxide ligand sites. In the solid-state structure of 3 it is rather unusual that the Na-p2-0 distances are longer than the Na-p3-O distances. One might expect these values to show the same behavior as the alkoxides bridging the thorium atoms: p3-OR > p2-OR > OR. Long p3-O bonds of an [M2(OR)9]- fragment bound to a heterometal center are a common feature seen in the chemistry of the [Zr2(0-i-Pr)g]- unit, and the long bonding interactions of Cotton, F. A,; Marler, D. 0.;Schwotzer, W. Inorg. Chem. 1984, 23, 4211. Cotton, F. A.; Marler, D. 0.;Schwotzer, W. Inorg. Chim. Acta 1984, 95,207. Cotton, F. A.; Marler, D. 0.;Schwotzer, W. Inorg. Chim. Acta 1984, 95, L23. Evans, W. J.; Sollberger, M. S.Inorg. Chem. 1988, 27, 4417. Evans, W. J.; Sollberger, M. S.; Hanusa, T. P. J. Am. Chem. SOC.1988, -/ i- n- ., 1841. --
Bradley, D. C.; Chudzynska, H.; Hursthouse, M. B.; Motevalli, M. Polyhedron 1991, 10, 1049. Chisholm, M. H.; Folting, K.; Huffman, J. C.; Kirkpatrick,C. C. J. Am. Chem. SOC.1981, 103, 5967. Vaarstra, B. A.; Streib, W. W.; Caulton, K. G. J. Am. Chem.SOC.1990, 112, 8593. Sogani, S . ; Singh, A.; Bohra, R.; Mehrotra, R. C.; Nottenmeyer, M. J. Chem. SOC.,Chem. Commun. 1991, 738. Coan, P. S.; Streib, W. E.; Caulton, K. G. Inorg. Chem. 1991,30, 5019. Vaarstra, B. A.; Huffman, J. C.; Streib, W. E.; Caulton, K.G. Inorg. Chem. 1991, 30, 3068.
Clark and Watkin
1770 Inorganic Chemistry, Vol. 32, No. 9, 1993
the p3 alkoxides are presumably due to a loss of electron density at oxygen with each successive bridge.27,28J0However, Cotton's structure of KU2(O-t-Bu)9 shows the same trend as NaThs(0t-Bu)g; the K-0 distances are 2.94 and 2.75 A for doubly and triply bridging alkoxides.21 In the two actinide structures, there is no terminal ligand attached to the alkali metal atom, while in the zirconium complexes, such as [BaZr2(O-i-Pr)lo]230 and (DME)KZr2(O-i-Pr)9,27there are other ligands attached to the heterometal atom. These additional ligands may tend to pull the heterometal center away from the Zrz unit. To test this, we performed some simple trigonometric calculations on the NaTh2(O-r-Bu)9structural unit. By leaving all atoms in place and simply pulling the sodium atom away from the Th-Th vector to make an equilateral triangle (Th-Th = Th-Na = 3.732 A), one finds that the Na-p20 distance lengthens from 2.60 to 2.74 A, while the Na-p3-0 distance increases more dramatically from 2.40 to 2.75 A. The fact that the triply bridging Na-0 distances are shorter than the doubly bridging ligands appears to be simply geometrical. In the actinide structures with no other terminal ligand attached to the alkali metal atom, this atom is apparently tucked in tighter to the "basket" formed by the four oxygen atoms. Terminal Th-O distances for both structures reported here are rather short, and the corresponding Th-0-C angles are large, ranging from 158.2 to 171.6". Similar trends have been observed in early transition metal alkoxide compounds, where short M - O bonds and large M-0-C angles have been taken as structural evidence for oxygen-to-metal a-donation from alkoxide ligands.31 Indeed, this is a commonly accepted phenomenon in early transition metal alkoxide and aryloxide c h e m i ~ t r y . ~However, ~J~ a recent publication on four-coordinate aluminum alkoxides revealed that M-0 bond length and M-O ?r bond order do not necessarily ~orrelate.~3 A very short metal-oxygen bond may result from a high degree of ionic character or alternatively from multiple bonding, 0 p r to M d r . More electropositive metals in their highest oxidation states such as A13+,Zr4+,or Th4+might be expected to be more ionic in character than later, less electropositive d-block elements in the mid transition series. However, we note that in the case of transition elements, the short M-0 bonds associated with r-bonding interactions are always accompanied by an obtuse M-O-C angle, while in fourcoordinate aluminum alkoxides (no accessible d orbitals and little to no M-0 r-bonding) short M-0 distances are accompanied by more acute M-0-C angles ranging from 135 to 150°.34 In addition, theoretical and spectroscopic studies have shown that empty thorium 6d orbitals are very 10w-lying3~and therefore should be available for M-0 *-bonding interactions. The trends in bond distances and angles seen in 1,3, and Thz(OCH-i-Pr2)g may serve as structural evidence for some degree of oxygen-tometal *-bonding in thorium alkoxides. SpectroscopicCharacterization. Room-temperature IH NMR spectra reveal only one type of alkoxide ligand for Th(0-tB ~ ) ~ ( p y(1) ) z presumably due to a fluxional process in solution. Low-temperature (-75 "C) spectra in toluene-& failed to freeze out a limiting structure. The room-temperature 'H NMR spectrum of Th2(O-t-Bu)8(HO-t-Bu) (2) in benzene-& shows only one broad t-Bu signal (6 1.54) and a broad resonance at 6 3.22, which we assign as the alcoholic OHproton. The intensity (31) Chisholm, M. H. Polyhedron 1983, 2, 681. Chisholm, M. H.; Clark, D. L. Comments Inorg. Chem. 1987, 6, 23. (32) Coffindaffer, T. W.;Steffy, B. D.; Rothwell, I. P.; Folting, K.; Huffman, J. C.; Streib, W. E. J. Am. Chem. Soc. 1989, 111, 4742. (33) Cayton, R. H.; Chisholm, M. H.; Davidson, E. R.; DiStasi, V. F.; Du, P.; Huffman, J. C. Inorg. Chem. 1991, 30, 1020. (34) For a tabulation of terminal AI-0 distances and AI-0-C angles in four-coordinate aluminum alkoxides, see: Evans, W. J.; Boyle, T. J.; Ziller, J. W. Polyhedron 1992, I I , 1093. (35) Bursten, B. E.; Rhodes, L. R.; Strittmatter, R. J. J. Less-Common Met. 1989, 149, 207. Ionova, G. V.; Pershina, V. G.;Spitsyn, V. I. Dokl. Akad. Nauk SSSR 1982, 263, 130. Hessler, J. P.; Carnall, W. T. In Lanthanide and Actinide Chemistry and Spectroscopy; Edelstein, N. M., Ed.; American Chemical Society: Washington, DC, 1980.
ratio of these two signals is ca. 8O:l consistent with these assignments. The exact position of the OH resonance changes as a function of solvent and concentration, consistent with our expectations of an alcoholic OHproton. We were unable to freeze out a static structure for 2 in toluene-ds in the temperature range +25 to -90 O C presumably due to rapid proton scrambling and/ or alkoxide site exchange. Room-temperature IH NMR spectra of NaTh2(O-t-Bu)9 (3) displayed four types of alkoxide ligands in a static 4:2:2:1 ratio consistent with our expectations on the basis of the solid-state molecular structure. In the case of Th30( 0 - t - B ~ (4), ) ~ ~IH N M R spectroscopy revealed a static 3:3:3:1 pattern of tert-butoxide resonances indicative of the well-known M 3 0 ( 0 R ) structural unit.16,26 During the course of our studies of thorium alkoxide complexes and their Lewis base adducts, we have found that the chemical shift of the ortho protons of a pyridine ligand bound to thorium are very sensitive to coordination environment. As a result, one can readily follow the course of the reaction between pyridine and thealcoholatedimerTh2(O-t-Bu)9(HO-t-B~) (2) by IHNMR spectroscopy at ambient temperatures. When less than 1 equiv of pyridine per thorium atom is added, a single ortho pyridine resonance at 6 = 8.95 ppm is observed by IH NMR spectroscopy. When greater than 1 equiv of pyridine is added, a second ortho resonance is observed to grow in at 6 = 8.53 ppm. As the pyridine titration continues, theoriginalortho resonancebegins todisappear as the new resonance grows in until exactly 2 equiv of pyridine perthoriumhas beenadded. At thispoint, the'HNMRspectrum of the product is identical to that observed for Th(O-t-B~)~(py)2 (1). We take this as evidence for the displacement of coordinated HO-t-Bu in 2 by pyridine to form a new dimer Th2(O-t-Bu)s(py)2 (S), which can react with additional added pyridine to produce monomeric Th(O-t-Bu)4(py)2 (1) as outlined in eq 8. The molecular geometry indicated for Thz(O-t-Bu)s(py)2 (5) in eq 8 is based on the structure that we have observed in the solid state for Th2(0CHEt~)8(py)2.~~
2
5
1
Concluding Remarks During the course of our studies we have been unable to isolate and characterize a homoleptic T h ( 0 - ~ - B Ucomplex, )~ consistent with the observations of Sattelberger and co-workers in their studies on the uranium tert-butoxide system.16 We have shown that one can readily isolate well-characterizable monomeric, dimeric, or trimeric tert-butoxide complexes depending upon reaction conditions. It seems clear that octahedral coordination is the preferred coordination environment for the tert-butoxide ligand around thorium, and octahedral coordination has been found exclusively in the actinide, lanthanide, and yttrium tertbutoxide structures reported to date.1v22-25-37 In the absence of added base, the dimeric six-coordinate alcoholate Th2(O-tBu),(HO-t-Bu) is formed, and this is consistent with uranium and lanthanum tert-butoxide chemistry where polymetallic alcoholates of formulas U ~ ( O - ~ - B U ) ~ ( H O - ~and - B ULa3(O-t) (36) Barnhart, D. M.;Clark, D. L.; Huffman, J. C.; Watkin, J. G. Manuscript in preparation. (37) Marks, T. J.; Ernst, R. D. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: London, 1982; Chapter 21. Forsberg, J. H.; Moeller, T. In Gmelin Handbook of Inorganic Chemistry, 8th ed.; Moeller, T., Kruerke, U., Schleitzer-Rust, E., Eds.; Springer-Verlag: Berlin, 1983; Part D6, pp 137-282. Schumann, H.; Genthe, W. In Handbook on the Physics and Chemistry of Rare Earths; Gschneidner, K. A., Jr., Eyring, L., Eds.; Elsevier: Amsterdam, 1985; Vol. 7, Chapter 53 and references therein. Mehrotra, R. C.; Singh, A.;Tripathi, U.M. Chem. Rev. 1991,91,1287. Evans, W. J.; Foster, S. E. J. Organomet. Chem. 1992, 433, 79.
Thorium tert-Butoxide Complexes Bu)g(HO-t-Bu)Zare formed.I6J5 In the presence of a good donor ligand such as pyridine, the alcoholate dimer is cleaved to produce monomeric Th(O-t-B~)~(py)~. This is incontrast to thechemistry of yttrium complexes in which the trimetallic structure of Y3(O-t-Bu)7C12(THF)zis characteristically retained in reactions of yttrium tert-butoxide complexe~.*~-~~~38 In the solid-state structures of 1 and 3, the relatively short Th-O bonds, obtuse Th-O-C angles, and cis-pyridineligands may serve as structural evidence for some degree of oxygen-to-metal a-bonding in aliphaticthorium alkoxideswhere virtual 6d orbitalsare expected to be low-lying and available for such interactions. During Bradley'spioneering workon the thorium tert-butoxide system in 1954, tert-butoxidecomplexeswere preparedvia alcohol interchange employing tert-butyl alcohol as solvent.2 On the basis of the results reportedhere, it seems likely that such reaction conditions would favor Thz(O-t-Bu)8(HO-t-Bu) as the major product. However,we have not tested Bradley's preparative route since the exact nature of the Th(O-i-Pr)4starting material is still somewhat uncertain. But we have shown that Thz(0-~-BU)~(HO-t-Bu) is susceptible to hydrolysis to give trimetallic Th30(O-t-Bu)lo. Since ebulliometricmolecularweight determinations can take some time to establish equilibrium, it is possible that Th3O(O-t-Bu) was the solution species which gave a molecular complexity of 3.4 in Bradley's original studies.z We plan to test this hypothesis when we have completed our characterization of Th(O-i-Pr)4 compounds.
Inorganic Chemistry, Vol. 32, No. 9, 1993 1771 (m), 1355 (s), 1225 (m), 1205 (s), 1190 (s), 1070 (w), 1035 (w), 1023 (w), 987 (s), 962 (s), 931 (w). 912 (s), 830 (w), 772 (m), 756 (w), 727 (w), 701 (m), 622 (w), 614 (w), 524 (w), 497 (s), 480 (m). Anal. Calcd for C26H~gN~04Th:C, 45.74; H, 6.79; N, 4.10. Found: C, 45.38; H, 6.61; N, 5.06. ThZ(O-t-Bu)8(H-O-t-Bu) (2). In the drybox, 4.00 g (5.62 mmol) of
-
thorium metallacycle [((M~~S~)ZN}~T~(CH~SIM~ZNS~M~~)] was dissolved in 100 mL of toluene in a 250-mL Erlenmeyer flask. To the stirred thorium solution was then added dropwise a solution of 1.88 g (25.4 mmol) of tert-butyl alcohol in 10 mL of toluene. The mixture was stirred at room temperature for 24 h, and then all solvent was removed in uucuo to leave a white solid. This solid was taken into 100 mL of hexane, and the mixture was filtered through a Celite pad. The volume of the filtrate was reduced to 15 mL and cooled to -40 OC, producing a mass of white crystals overnight. The crystals were decanted free from solvent and allowed to dry. Yield: 2.20 g (70%). ' H NMR (300 MHz, C&): 8 3.22 (br, lH, OH), 1.54 (s, 81H, t-Bu). ' H NMR (250 MHz, C~DP,): 6 2.87 (br, lH, OH), 1.53 (s, 81H, t-Bu). IR (KBr plates, Nujol mull): 3171 (w), 1465 (s), 1365 (m), 1354 (m), 1227 (s), 1203 (s), 1188 (s), 1047 (w), 985 (s), 960 (s), 910 (s), 771 (m), 758 (m), 727 (w), 523 (w), 495 (s), 479 (s). Anal. Calcd for C36Hs109NaTh2: C, 38.50; H, 7.36; N, 0.00. Found: C, 38.52; H, 7.70; N, 0.03. NaThZ(0-t-Bu)g (3). In the drybox, 0.79 g (0.70 mmol) of Th2(0-t-Bu)g(HO-t-Bu) was dissolved in 50 mL of toluene in a 125-mL Erlenmeyer flask. Then 0.128 g (0.70 mmol) of solid sodium bis(trimethylsily1)amidewas added to the stirring thorium solution, and stirring continued at room temperature for 16 h. All solvent was removed in vacuo to leave a white solid, which was dissolved in 50 mL of hexane and filtered through a Celite pad. The volume of the filtrate was reduced to 10 mL and placed at -40 OC, producing colorlesscubiccrystalsovernight. Experimental Section The crystals were filtered off and allowed to dry. Yield: 0.59 g (73%). ' H NMR (300 MHz, C6D6): 6 1.71 (s, lH), 1.69 (s, 2H), 1.53 (s, 4H), General Procedures and Techniques. All manipulations were 1.26 (s, 2H). IR (Nujol mull, KBr plates): 1364 (s), 1355 (s), 1223 (s). carried out under an inert atmosphere of oxygen-free UHP grade 1202 (s), 1188 (s), 1046 (m), 1019 (w), 983 (s), 958 (s), 910 (s), 769 argon using standard Schlenk techniques or under oxygen-free (m), 756 (sh), 692 (w), 523 (m), 495 (s), 479 (m). Anal. Calcd for helium in a Vacuum Atmospheres glovebox. ThI4(THF)4,I3 C36H~lNaO9Th2:C, 37.76; H, 7.13; N, 0.00. Found: C, 37.20; H, 6.07; N, 0.12. [((M~,S~)~N)~T~(CH~SIM~~NS~M~~)]?~ and NaN(SiMe3)z40were prepared as described previously. Potassium tert-butoxide was prepared by Th30(0-t-Bu)lo (4). In the drybox, 3.00 g (4.21 mmol) of thorium thereactionof potassium hydridewith tert-butyl alcoholin THF. Solvents, metallacycle was dissolved in 75 mL of toluene in a Schlenk reaction except for pyridine, were degassed and distilled from Na/K alloy under vessel, and 1.41 g (19.02 mmol) of dry tert-butyl alcohol added. The nitrogen. Pyridine was distilled from CaH2 under argon. tert-butyl flask was removed from the drybox and attached to a Schlenk line, and alcohol was distilled from sodium and stored in the drybox. Benzene-& 50 pL (0.90 mmol) of water was added via a microliter syringe. The and toluene-& were degassed, dried over Na/K alloy, and then trapsolution was then refluxed under argon for 48 h and returned to the to-trap distilled before use. Solvents were taken into the glovebox, and drybox. All solvent was removed in uucuo to leave a white solid residue, a small amount was tested with a solution of sodium benzophenone in which was extracted into 100 mL of hexane and filtered through a Celite THF. Solvents that failed to maintain a purple coloration from this test pad. The volume of the filtrate was reduced to ca. 75 mL and placed were not used. at -40 "C, producing a fluffy crystalline mass over a several days. This NMR spectra were recorded at 22 OC on Bruker WM 300 or AF 250 solid was filtered off and dried invacuo. Yield: 0.58 g (29%). IH NMR spectrometers in benzene-d6 or toluene-ds. All ' H NMR chemical shifts (250 MHz, C&): 6 1.80 (S, 9H), 1.74 (S, 27H), 1.46 (s, 27H), 1.45 (s, are reported in ppm relative to the ' H impurity in benzene-d6 or toluene27H). IR (Nujol mull, KBr plates): 1364 (s), 1356 (s), 1238 (m, sh), ds set at 6 7.15 or 2.09, respectively. Infrared spectra were recorded on 1227 (m), 1196 (s), 991 (m), 964 (s), 913 (s), 771 (m), 761 (sh), 668 a Perkin-Elmer 1500 spectrophotometer interfaced with a 1502 central (w), 529 (m), 497 (s), 480 (m). Anal. Calcd for C40H90011Thj:C, processor. Elemental analyses were performed on a Perkin-Elmer 2400 33.29; H, 6.29; N, 0.00. Found: C, 33.27; H, 6.09; N, 0.01. CHN analyzer. Elemental analysis samples were prepared and sealed Crystallographic Studies. Th(O-t-Bu)4(py)Z (1). Crystal data, colin tin capsules in the glovebox prior to combustion. lection, and processing parameters are given in Table I. A crystal Syntheses. Th(O-t-Bu)d(py)* (1). In the drybox, 7.00 g (6.81 mmol) measuring 0.15 X 0.15 X 0.25 mm was mounted in a sealed quartz of ThI4(THF)4 was dissolved in 100 mL of THF in a 250-mL Erlenmeyer Lindemann tube and placed on the goniometer head of an Enraf-Nonius flask and 10 mL of pyridine added. Then a solution of 3.15 g (28.1 CAD-4 diffractometer with graphite-monochromated Mo K a radiation. mmol) of potassium tert-butoxide in 20 mL of THF was added to the Unit cell parameters were determined from the least-squares refinement flask to produce a white precipitate. This suspension was allowed to stir of ((sin 8)/X)2 values for 24 accurately centered reflections. Three at room temperature for 24 h before being filtered through a Celite pad reflections were chosen as intensity standards and were measured every to give a clear, pale yellow filtrate. All solvent was removed in uucuo to 3600 s of X-ray exposure time, and three orientation controls were leave a pale yellow solid, which was dissolved in 80 mL of 15:l hexane/ measured every 250 reflections. Data were collected by w scans. pyridine and filtered again through a Celite pad. The volume of the The intensities were corrected for Lorentz and polarization effects, filtrate was reduced to 20 mL and placed at -40 OC. Overnight, colorless and an empirical absorption correction based on azimuthal scans was crystals were deposited. These were filtered off and allowed to dry. applied. Equivalent reflections were merged, and systematically absent Yield: 1.04 g (22%). IH NMR (300 MHz, C6D6): 6 8.53 (br, 2H, ortho reflections were rejected. The structure was solved by routine Patterson py),6.96(brm,lH,parapy),6.65(m,2H,metapy),1.60(~,18H,t-Bu).and Fourier methods. During the initial least-squares refinement it became IR (Nujol mull, KBr plates): 1600 (w), 1595 (w), 1445 (sh, m), 1365 evident that there was a disorder problem in the three methyl carbons attached to C(5). Least-squares refinement varying the occupancies of (38) Evans, W. J.; Boyle, T. J.; Ziller, J. W. Presented at the 203rd National these carbons indicated two sets of three methyl carbons with 57% and Meeting of the American Chemical Society, San Francisco, CA, April 43% occupancy. The occupancy was then fixed, and the least-squares 1992; INOR 702. refinement was completed. After inclusion of anisotropic thermal (39) Dormond, A.; El Bouadili,A.; Aaliti, A,; Moise, C. J . Organomet. Chem. parameters for all non-hydrogen atoms and geometrical generation of 1985, 288, C 1 hydrogen atoms which were constrained to 'ride" upon the appropriate (40) Kriiger, C. R.; Niederpriim, H. Inorg. Synth. 1966, 8, 15.
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I
1772 Inorganic Chemistry, Vol. 32, No. 9, 1993 carbon atoms, final refinement using 2570 unique observed [F> 4a(F)] reflections converged at R = 0.040 and R, = 0.055 (where w = [a(F) + 0.000625(F)2]-1). No hydrogen atoms were included on the disordered carbons C(6), C(7), or C(8). All calculations were performed using the SHELXTL PLUS suite of computer programs (Siemens Analytical X-ray Instruments, Inc., 1990). NaTh2(0-&Bu)s (3). Crystal data, collection, and processing parameters are given in Table I. A crystal measuring 0.35 X 0.25 X 0.65 mm was mounted in a sealed quartz Lindemann tube and placed on the goniometer head of an Enraf-Nonius CAD-4 diffractometer with graphitemonochromated Mo K a radiation. Unit cell parameters were determined from the least-squares refinement of ((sin 6')/A)2 values for 24 accurately centered reflections. Three reflections werechosen as intensity standards and were measured every 3600 s of X-ray exposure time, and three orientation controls were measured every 250 reflections. Data were collected by w scans. The intensities were corrected for Lorentz and polarization effects, and an empirical absorption correction based on azimuthal scans was applied. After inclusion of anisotropic thermal parameters for all non-
Clark and Watkin hydrogen atoms and geometrical generation of hydrogen atoms which were constrained to "ride" upon the appropriate carbon atoms, final refinement using 2448 unique observed [F>6o(F)] reflections converged at R = 0.038 and R, = 0.054 (where w = [u2(F)+ 0.000625(F)2]-1).All calculationswere performed using theSHELXTL PLUS suiteofcomputer programs (Siemens Analytical X-ray Instruments, Inc., 1990).
Acknowledgment. We wish to thank Drs. A. P. Sattelberger, W. G. Van Der Sluys, K. G. Caulton, and S.G. Bott for helpful discussions. We acknowledgethe Officeof Basic Energy Sciences, Division of Chemical Sciences, U.S.Department of Energy, under Contract No. W-7405-eng-36, and the Yucca Mountain Site Characterization Project Office for financial support. Supplementary Material Available: Tables of anisotropic thermal parameters and hydrogen atom coordinates for Th(O-?-Bu)dpy2 and NaThz(O-t-Bu)g (3 pages). Ordering information is given on any current masthead page. Structure factor tables are available from the authors upon request.
